CN105418895B - Thiophene is the preparation for the bioxindol conjugated polymer that space isolates group, purposes - Google Patents
Thiophene is the preparation for the bioxindol conjugated polymer that space isolates group, purposes Download PDFInfo
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Abstract
The invention provides the preparation that a kind of thiophene is the bioxindol conjugated polymer that space isolates group, purposes；The structure of the conjugated polymer is as shown in Formulas I or Formula II：Wherein R1、R2It is independently each C respectively8~C20Alkyl chain, 100 >=n ﹥ 1.Synthetic method provided by the invention is simple to operate, cost of material is low.Conjugated polymer prepared by the present invention can be used as semiconducting organic layer to be applied in polymer solar battery test；Material can be processed with solution, and ultraviolet spectra absorbs excellent, and film photovoltaic device test shows that polymeric material can apply to film photovoltaic device active layer, in the device detection of inverted structure, energy conversion efficiency 1.51%.
Description
Technical field
The present invention relates to the organic semiconductor material field of a kind of solution processable, is related to a kind of thiophene and isolates base for space
The preparation of the bioxindol conjugated polymer of group, purposes.
Background technology
Modern society increasingly increases the demand of the energy, and oil, coal, natural gas etc. are all non-renewable energy resources, increasingly
Exhaustion, development development solar cell utilize the effective way that solar energy is the energy problem that solution human society faces.
Bioxindol is a kind of important electron donor in polymer thin-film solar, because it has the good purples of C=C
External spectrum absorbent properties, good solubility, application is very extensive in OPV (organic photovoltaic material), but C=C both sides
Not in one plane, but there is certain bending in indolyl radical, have impact on the planar conjugate of bioxindol, constrain photovoltaic
The further raising of performance.
Isolate group bioxindol by space of thiophene the invention provides one kind, effectively solve this problem.So as to
The good photovoltaic material of flatness is obtained, this development to OPV materials has great importance.
The content of the invention
For in the prior art the defects of, it is an object of the invention to provide a kind of thiophene be space isolate group bioxindol
The preparation of conjugated polymer, purposes.The good photovoltaic material of flatness is obtained, this development to OPV materials has important meaning
Justice.
The purpose of the present invention is achieved through the following technical solutions：
In a first aspect, the present invention relates to the bioxindol conjugated polymer that a kind of thiophene is space isolation group, its structural formula
As shown in Formulas I or Formula II：
Wherein R1、R2It is independently each C respectively8~C20Alkyl chain, 100 >=n ﹥ 1.
Second aspect, the present invention relates to the bioxindol that a kind of thiophene as claimed in claim 1 is space isolation group to be total to
The preparation method of conjugated polymer, the preparation method of the conjugated polymer are：Using dry toluene as solvent, compound HIIDTWith double methyl tin benzene thiophenesGeneration Stille coupling reactions, polymerization
Obtain Formulas I in claim 1 or the conjugated polymer shown in Formula II；Wherein described R1、R2C is respectively respectively8~C20Alkyl chain.
Preferably, the preparation of the compound HIIDT comprises the following steps：
S1, compound R1- I or R1- Br reacts with 6- bromo-isatins, generates compound 1Wherein R1
For C8~C20Alkyl chain；
S2, compound 1 slough a carbonyl under the reduction of hydrazine hydrate, generate compound 2Its
Middle R1For C8~C20Alkyl chain；
S3,2,5- dibromo thiophenes generate compound 3 in the presence of n-BuLi and N, N '-dimethyl formamide
S3, using absolute methanol as solvent, pyridine is catalyst, compound 2 and the reaction generation compound of compound 3 HIIDT.
Preferably, in step S1, the compound R1- I or R1The mol ratio of-Br and 6- bromo-isatins is 1：1~4:1, instead
It is 60~120 DEG C to answer temperature.
Preferably, in step S2, the mass percent concentration of the hydrazine hydrate is 30%~99%, and the reaction temperature is
80~150 DEG C, the reaction time is 2~48 hours.
Preferably, in step S3,2, the 5- dibromo thiophenes：The mol ratio of n-BuLi is 1:2.2~1:3, N, N '-two
NMF is excessive；It is preferred that 2,5- dibromo thiophenes：N, N '-dimethyl formamide mol ratio are 1:3~1:5；It is described anti-
It is -78 DEG C to answer temperature, and the reaction time is 62~24 hours.
Preferably, in step S4, the mol ratio of the compound 2 and compound 3 is 2.2:1~3:1, reaction temperature 60
~120 DEG C, the reaction time is 6~24 hours.
Preferably, the Stille coupling reactions with (three (dibenzalacetone) two palladium) for catalyst, (three (adjacent methyl)
Phenyl phosphorus) it is part, HIIDT is 1 with pair mol ratio of methyl tin benzene thiophenes:1~1：1.3 reaction temperatures are 60~120
DEG C, 1~24 hour reaction time.
The third aspect, the present invention relates to the bioxindol that a kind of thiophene as claimed in claim 1 is space isolation group to be total to
Purposes of the conjugated polymer in organic photovoltaic devices are prepared, it is characterised in that the conjugated polymer is total to fullerene derivate
Mix up the purposes in polymer solar battery test for active layer.
Compared with prior art, the present invention has following beneficial effect：
1st, synthetic method provided by the invention is simple to operate, cost of material is low.
2nd, conjugated polymer prepared by the present invention can be used as semiconducting organic layer to be tested applied to polymer solar battery
In；Material can be processed with solution, and ultraviolet spectra absorption is excellent, and film photovoltaic device test shows that polymeric material can be applied
In film photovoltaic device active layer, the device detection of inverted structure, energy conversion efficiency 1.51%.
Brief description of the drawings
The detailed description made by reading with reference to the following drawings to non-limiting example, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is embodiment 1 polymer P HIIDT-BDTO and PHIIDT-BDTT synthetic route chart；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of the compound 1 of embodiment 1；
Fig. 3 is the nucleus magnetic hydrogen spectrum figure of the compound 2 of embodiment 1；
Fig. 4 is the nucleus magnetic hydrogen spectrum figure of the compound 3 of embodiment 1；
Fig. 5 is the compound HIIDT of embodiment 1 nucleus magnetic hydrogen spectrum figure；
Fig. 6 is embodiment 2 polymer P HIIDT-BDTO and PHIIDT-BDTT chloroformic solution and the ultraviolet suction of solid film
Receive spectrogram；
Fig. 7 is embodiment 2 polymer P HIIDT-BDTO and PHIIDT-BDTT cyclic voltammetry curve figure；
Fig. 8 is embodiment 2 polymer P HIIDT-BDTO and PHIIDT-BDTT thermogravimetric analysis spectrogram；
Fig. 9 is the polymer P HIIDT-BDTO and PHIIDT-BDTT and PC of embodiment 361BM is the film sun of semiconductor layer
The I-V curve figure of energy battery device.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1 prepares the bioxindol conjugated polymer that thiophene isolates group for space
This implementation provide a kind of thiophene for space isolate group bioxindol conjugated polymer (PHIIDT-BDTO and
PHIIDT-BDTT synthesis), its structural formula is as shown in table 1, and synthetic route is shown in Fig. 1.
Table 1
Comprise the following steps that：
(a) synthesis of compound 1
The structural formula of compound 1 is：
Wherein R1For 2- octyldodecyls.
The preparation method of compound 1：As shown in figure 1, by 6- bromo-isatins (2.26g, 10mmol), potassium carbonate (2.07g,
15mmol), the iodo- 2- octyldodecyls (4.90g, 12mmol) of 1- and DMF (50mL) are added in two-mouth bottle, the standby pressure of nitrogen, 80 DEG C
24h is reacted, is cooled to room temperature, 100mL watery hydrochloric acid stirring 2h is added, adds a large amount of water, dichloromethane extracts 3 times, merges organic
Phase, washed with saturated sodium-chloride, anhydrous MgSO4Dry, be spin-dried for solvent, petroleum ether：Dichloromethane is 3:1 (volume ratio) is elution
Agent, post separation is chromatographed, brown oil liquid (3.15g, 62%) is obtained after being spin-dried for.The nucleus magnetic hydrogen spectrum figure of the compound 1 of preparation is shown in
Fig. 2.
(b) synthesis of compound 2
The structural formula of compound 2 is：
Wherein R1For 2- octyldodecyls.
The preparation method of compound 2：As shown in figure 1, compound 1 (10g, 20mmol), hydrazine hydrate (85%, 150ml) add
Enter in bottle with two necks, nitrogen displacement 15min, standby pressure, flow back 24h, is cooled to room temperature, adds 200ml water and extracts 3 with dichloromethane
It is secondary, anhydrous Na2SO4Dry, filtering, be spin-dried for solvent, petroleum ether：Dichloromethane is 3:1 (volume ratio) is eluent, and chromatographic column divides
From obtaining weak yellow liquid (6.13g, 63%) after being spin-dried for.The nucleus magnetic hydrogen spectrum figure of the compound 2 of preparation is shown in Fig. 3.
(c) synthesis of compound 3
The structural formula of compound 3 is：
The preparation method of compound 3：As shown in figure 1,2,5- dibromo thiophenes (2.41g, 10mmol), tetrahydrofuran
(50ml), the standby pressure of -78 DEG C of nitrogen, is added dropwise n-BuLi (22ml, 22mmol), stirs 30 minutes, DMF (5ml), stirring 30 is added dropwise
Minute, room temperature reaction overnight, adds water, petroleum ether extraction 3 times, anhydrous sodium sulfate drying, leacheate petroleum ether：Ethyl acetate
(1:3) post separation is chromatographed.Obtain compound 3 (1.01g, 72%).The nucleus magnetic hydrogen spectrum figure of the compound 3 of preparation is shown in Fig. 4.
(d) compound HIIDT synthesis
Compound HIIDT structural formula is：
Wherein R1For 2- octyldodecyls.
HIIDT preparation method：As shown in figure 1, by compound 2 (1.08g, 2.2mmol), compound 3 (0.14g,
1mmol), pyridine (5ml), methanol (60ml) are added in bottle with two necks, are passed through nitrogen discharge air 15min, the standby pressure of nitrogen, backflow
24h, room temperature is cooled to, solvent is removed in rotation, adds water, watery hydrochloric acid, and dichloromethane extracts 3 times, merges organic phase, uses saturated sodium-chloride
Washing, anhydrous MgSO4Dry, be spin-dried for solvent, petroleum ether：Dichloromethane is 3:1 (volume ratio) is eluent, chromatographs post separation,
Red solid product (0.95g, 87%) is obtained after being spin-dried for.The compound HIIDT of preparation nucleus magnetic hydrogen spectrum figure is shown in Fig. 5.
(e) synthesis of the double tin monomers of midbody compound benzene thiophene
The structural formula of the double tin monomers of benzene thiophene is：
Its detailed preparation method is shown in document《Hwang,Y.J；Kim,F.S；Xin,H；Jenekhe,S.A；New
Thienothiadiazole-Based Conjugated Copolymers for Electronics and
Optoelectronics.Macromolecules 2012,45,3732-3739；Liao,S.H；Jhuo,H.J；Cheng,Y.S；
Chen,S.A；Fullerene Derivative-Doped Zinc Oxide Nanofi lm as the Cathode of
Inverted Polymer Solar Cells with Low-Bandgap Polymer(PTB7-Th)for High
Performance.Adv.Mater.2013,25,4766–4771.》
The composition principle of the double tin derivatives of Dithiophene：Li+The H atom of 2, thiophene on attack BDT rings, then with methyl tin
Generation electrophilic substitution reaction, it is unrelated with alkyl chain size and shape, so according to this reaction principle, different side chains can be synthesized
Double methyl tin BDT.
(f) polymer P HIIDT-BDTO synthesis
Under nitrogen atmosphere, by HIIDT (0.2186g, 0.2mmol) and the BDTO ((second of 2,6- bis- (tin trimethyl) -4,8- bis-
Base hexyl) benzene thiophene) (0.1544g, 0.2mmol) is poured into polymerization pipe, nitrogen displacement 10min, rapidly join catalyst
Pd2(dba)3(0.0037g, 0.0040mmol), part P (o-tol) 3 (0.0048g, 0.0160mmol), and solvent dry toluene
(10ml), nitrogen displacement 15min, quick tube sealing.65 DEG C, polyase 13 .5h are to slowly warm up to, is cooled to room temperature, is added appropriate anhydrous
Methanol and a few drop hydrochloric acid are precipitated, and after stirring 2h, filtering, obtain the graininess crude product with metallic luster.Product is successively
With methanol, petroleum ether and chloroform surname extraction, chloroform is spin-dried for, is precipitated in methyl alcohol, filtered, the graininess for obtaining metallic luster is total to
Polymers PHIIDT-BDTO (0.215g, 78%), number-average molecular weight 94.3kDa, molecular weight distribution 1.6, n=68.
(g) polymer P HIIDT-BDTT synthesis
Under nitrogen atmosphere, by HIIDT (0.2186g, 0.2mmol) and the BDTT ((5- of 2,6- bis- (tin trimethyl) -4,8- bis-
(2- ethylhexyls) thienyl -2-)-benzene thiophene) (0.1809g, 0.2mmol) is poured into polymerization pipe, nitrogen displacement
10min, rapidly join catalyst Pd2(dba)3(0.0037g, 0.0040mmol), part P (o-tol)3(0.0048g,
0.0160mmol), and solvent dry toluene (10ml), nitrogen displacement 15min, quick tube sealing.65 DEG C are to slowly warm up to, polymerization
2h, room temperature is cooled to, adds appropriate absolute methanol and a few drop hydrochloric acid are precipitated, after stirring 2h, filtering, obtain with metal light
The graininess crude product in pool.Product uses methanol, petroleum ether and chloroform surname extraction successively, is spin-dried for chloroform, precipitates in methyl alcohol, mistake
Filter, obtains granulated polymer PHIIDT-BDTT (0.220g, 74%), the number-average molecular weight 64.8kDa of metallic luster, point
Son amount is distributed as 1.6, n=43.
Embodiment 2, the ultra-violet absorption spectrum and electrochemistry that thiophene is the bioxindol conjugated polymer that space isolates group
Matter
The present invention relates to the polymer P HIIDT-BDTO and PHIIDT-BDTT of embodiment 1 in chloroformic solution and solid film
UV-vis absorption spectrums, referring to Fig. 6, PHIIDT-BDTO and PHIIDT-BDTT λ in chloroformic solutionmax absRespectively 609nm
And 602nm；The λ of the solid film of polymermax absRespectively：PHIIDT-BDTO 604nm and PHIIDT-BDTT 612nm, gather
Initial absorption peak (the λ of compoundonset abs) be respectively：PHIIDT-BDTO 720nm and PHIIDT-BDTT 730nm, optical energy band
Gap is respectively 1.72 and 1.70eV, and band gap is very narrow, is advantageous to improve Jsc.Fig. 7 give polymer P HIIDT-BDTO and
PHIIDT-BDTT cyclic voltammetry curve.Cyclic voltammetry test is enterprising in the CHI610D telephone wire analyzers of computer control
OK, using three traditional electrode test systems, platinum electrode is working electrode, and silver/silver ion electrode is reference electrode, and electrolyte is
The dichloromethane solution (0.1M) of tetra-n-butyl ammonium hexafluorophosphate, sweep speed 50mV/s, using ferrocene as reference.Ferrocene
The oxidizing potential measured under the system is 0.09eV, and because the energy level of ferrocene under vacuum condition is 4.8eV, the energy level of material can
It is calculated with the formula by following energy level：ELUMO=-(Ered,onset- 0.09+4.8) eV=- (Ered,onset+4.71)eV、EHOMO
=-(Eox,onset- 0.09+4.8) eV=- (Eox,onset+4.71)eV.The initial oxidation current potential of copolymer is respectively PHIIDT-
BDTO (+0.55V) and PHIIDT-BDTT (+0.56V), according to formula, the HOMO energy levels of copolymer are respectively PHIIDT-BDTO
(-5.26eV)、PDIIDT-BDTT(-5.27eV).Initial reduction current potential is respectively PHIIDT-BDTO (- 1.06V) and PHIIDT-
BDTT (- 1.03V), the lumo energy of copolymer is respectively PHIIDT-BDTO (- 3.65eV), PDIIDT-BDTT (- 3.68eV).
Fig. 8 is polymer P HIIDT-BDTO and PHIIDT-BDTT thermogravimetric analysis spectrogram, and it is fine to show that conjugated polymer has in figure
Heat endurance.
Embodiment 3 polymer P HIIDT-BDTO and PHIIDT-BDTT photovoltaic performance
The present embodiment is related to the polymer P HIIDT-BDTO and PHIIDT-BDTT of embodiment 1 as active layer material thin
Purposes in film solar cell.Using polymer P HIIDT-BDTO and PHIIDT-BDTT as donor material (D), fullerene
(PC71BM acceptor material (A)) is used as, using bulk heteroj unction structure test material photovoltaic performance.Polymer solar battery device
Part test transformation efficiency data are shown in Table 2, and I-V curve is shown in Fig. 9.The PHIIDT-BDTT transformation efficiencies of preliminary test are up to
1.51%.
Table 2
In summary, the synthetic method of present disclosure is easy and effective, and obtained subject polymer ultraviolet spectra absorbs strong
And it is wide, the processing of material solution processable, there is good application prospect in photovoltaic device.
It should be noted that when substituent R is other alkyl chains, although alkyl chain is different, experiment reaction condition and
Principle is identical, belongs to allogeneic reaction；When the n values of polymer depend on raw material donor donor with acceptor amount ratio and reaction
Between etc., it can be seen from general knowledge known in this field, n takes 100 >=n ﹥ 1 to be applied to the present invention.N is too big, then polymer molecular weight
Just too big, polymer is difficult to solvent, is also unfavorable for making devices and improves efficiency.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (9)
1. a kind of thiophene is the bioxindol conjugated polymer that space isolates group, it is characterised in that its structural formula such as Formulas I or Formula II
It is shown：
Wherein R1、R2It is independently each C respectively8~C20Alkyl chain, 100 >=n ﹥ 1.
2. a kind of thiophene as claimed in claim 1 is the preparation method for the bioxindol conjugated polymer that space isolates group, its feature exists
In the preparation method of the conjugated polymer is：Using dry toluene as solvent, compound HIIDT
With double methyl tin benzene thiophenesOccur
Stille coupling reactions, polymerization obtain Formulas I in claim 1 or the conjugated polymer shown in Formula II；Wherein R1、R2It is respective respectively
For C8~C20Alkyl chain.
3. thiophene as claimed in claim 2 is the preparation method for the bioxindol conjugated polymer that space isolates group, its feature
It is, the preparation of the compound HIIDT comprises the following steps：
S1, compound R1- I or R1- Br reacts with 6- bromo-isatins, generates compound 1Wherein R1For C8
~C20Alkyl chain；
S2, compound 1 slough a carbonyl under the reduction of hydrazine hydrate, generate compound 2Wherein R1
For C8~C20Alkyl chain；
S3,2,5- dibromo thiophenes generate compound 3 in the presence of n-BuLi and N, N '-dimethyl formamide
S4, compound 2 and the reaction generation compound of compound 3 HIIDT.
4. thiophene according to claim 3 is the preparation method for the bioxindol conjugated polymer that space isolates group, it is special
Sign is, in step S1, the compound R1- I or R1The mol ratio of-Br and 6- bromo-isatins is 1：1~4:1, the reaction temperature
Spend for 60~120 DEG C.
5. thiophene according to claim 3 is the preparation method for the bioxindol conjugated polymer that space isolates group, it is special
Sign is, in step S2, the mass percent concentration of the hydrazine hydrate is 30%~99%, and the reaction temperature is 80~150
DEG C, the reaction time is 2~48 hours.
6. thiophene according to claim 3 is the preparation method for the bioxindol conjugated polymer that space isolates group, it is special
Sign is, in step S3, the mol ratio of 2, the 5- dibromo thiophenes and n-BuLi is 1:2.2~1:3,2,5- dibromo thiophenes：
N, N '-dimethyl formamide mol ratio are 1:3~1:5；The reaction temperature is -78 DEG C, and the reaction time is 62~24 hours.
7. thiophene according to claim 3 is the preparation method for the bioxindol conjugated polymer that space isolates group, it is special
Sign is, in step S4, the mol ratio of the compound 2 and compound 3 is 2.2:1~3:1, the reaction temperature be 60~
120 DEG C, the reaction time is 6~24 hours.
8. thiophene according to claim 2 is the preparation method for the bioxindol conjugated polymer that space isolates group, it is special
Sign is, the Stille coupling reactions using three (dibenzalacetone) two palladium as catalyst, three (o-methyl-phenyl) phosphorus be with
The mol ratio of body, compound HIIDT and double methyl tin benzene thiophenes is 1:1~1：1.3, reaction temperature is 60~120 DEG C, instead
1~24 hour between seasonable.
9. a kind of thiophene as claimed in claim 1, which is the bioxindol conjugated polymer of space isolation group, is preparing organic photovoltaic
Purposes in device, it is characterised in that the blending of the conjugated polymer and fullerene derivate as active layer in polymer too
Purposes in positive energy battery testing.
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| CN104017187A (en) * | 2013-02-28 | 2014-09-03 | 海洋王照明科技股份有限公司 | Isoindigo group-containing polymer as well as preparation method and application thereof |
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|---|
| Antitumor activity and COMPARE analysis of bis-indole derivatives;Andreani A,et al;《Bioorganic and medicinal chemistry》;20100329;第18卷(第9期);第3004-3011页 * |
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